Inorganic Chemistry Commons^™

Modified Seed Growth Of Iron Oxide Nanoparticles In Benzyl Alcohol: Magnetic Nanoparticles For Radio Frequency Hyperthermia Treatment Of Cancer, Stanley E. Gilliland Iii

Theses and Dissertations

Iron oxide nanoparticles have received sustained interest for biomedical applications as synthetic approaches are continually developed for precise control of nanoparticle properties. This thesis presents an investigation of parameters in the benzyl alcohol synthesis of iron oxide nanoparticles. A modified seed growth method was designed for obtaining optimal nanoparticle properties for magnetic fluid hyperthermia. With a one or two addition process, iron oxide nanoparticles were produced with crystallite sizes ranging from 5-20 nm using only benzyl alcohol and iron precursor. The effects of reaction environment, temperature, concentration, and modified seed growth parameters were investigated to obtain precise control over properties …

Electron And Ion Spectroscopy Of Metal Hydrocarbon Complexes, Sudesh Kumari

Theses and Dissertations--Chemistry

Metal-hydrocarbon complexes were prepared in a laser-vaporization molecular beam source and studied by single-photon zero electron kinetic energy (ZEKE) and mass-analyzed threshold ionization (MATI) spectroscopy. The ionization energies and vibrational frequencies of the metal complexes were measured from the ZEKE and MATI spectra. Metal-ligand bonding and low-lying electronic states of the neutral and ionized complexes were analyzed by combining the spectroscopic measurements with quantum chemical calculations and spectral simulations.

In this dissertation, the metal complexes of mesitylene, aniline, cyclooctatetraene, benzene, ethene, and propene were studied. For each complex, different effects from metal coordination have been identified. Although metal-bis(mesitylene) sandwich complexes …

Salen Aluminum Compounds In The Dealkylation And Detection Of Organophosphates, Rahul R. Butala

Theses and Dissertations--Chemistry

The focus of this dissertation is the use of aluminum Schiff base compounds, Salen(^tBu)AlBr (SAB), in the dealkylation and detection of organophosphates (OPs). Three SAB compounds, Salen(^tBu)AlBr (1), Salpen(^tBu)AlBr (2), and Salophen(^tBu)AlBr (3) were used to dealkylate a variety of trialkyl OPs. These reactions lead to unique organic-soluble aluminum phosphate compounds containing six-coordinate aluminum. Examples include [salen(^tBu)AlOP(O)(OCH₃)₂]_n (4), [salen(^tBu)AlOP(O)(OCH₂CH₃)₂]_n (5), [salen(^tBu)AlOP(O)(OPh)₂]_{n …}

High Yield Solvothermal Synthesis Of Hexaniobate Based Nanocomposites Via The Capture Of Preformed Nanoparticles In Scrolled Nanosheets, Shivaprasad Reddy Adireddy

LSU New Orleans Theses and Dissertations

The ability to encapsulate linear nanoparticle (NP) chains in scrolled nanosheets is an important advance in the formation of nanocomposites.These nanopeapods (NPPs) exhibit interesting properties that may not be achieved by individual entities. Consequently, to fully exploit the potential of NPPs, the fabrication of NPPs must focus on producing composites with unique combinations of morphologically uniform nanomaterials. Various methods can produce NPPs, but expanding these methods to a wide variety of material combinations can be difficult. Recent work in our group has resulted in the in situ formation of peapod-like structures based on chains of cobalt NPs. Building on this …

Mechanistic Studies Of Bimolecular Electron Transfer Self-Exchange Rates Of Ruthenium Ammine Pyridyl Complexes Measured By Nmr Line Broadening Techniques, Yishun Qin

Master's Theses

The electron transfer (ET) self-exchange rates on a series of complexes of (NH₃)₅Ru^II/III L^2+/3+ in D₂O (where L is a substituted pyridyl ligand) were investigated by dynamic NMR measurements. Significant rate enhancement was observed for the cases of L = 3-phenylpyridine and 4-phenylpridine due to possible π-π stacking between Phpy ligands. These observations matche well with recent stopped-flow work by Mehmood on a similar set of related pseudo-self exchange reactions. Kinetics of the (NH₃)₅Ru^II/III (3-trifluoromethylpyridine)^2+/3+ self-exchange reactions with addition of various simple/complex salts and hexacyano salts …

Synthesis And Characterization Of Manganese Pyridazyl Complexes, Sana Shah

Masters Theses & Specialist Projects

Heterocyclic’s and their fused-ring derivatives have been of interest for their use in electronic materials due to their ease of production, synthetic versatility, and low cost compared to traditional inorganic materials like silicon. Pyridazines have been found to be useful in catalysis gas storage, polymeric sensors and biological mimetics. When a transition-metal is fused into a synthesized pyridazine, unique properties such as conductivity and optics are allowed. In this work, synthesized pyridazine complexes will be analyzed by mass spectroscopy, elemental analysis, nuclear magnetic resonance, imaging, x-ray crystallography, and infrared spectroscopy. We are interested in synthesizing organometallic pyridazines and manganese pyridazyl …

Synthesis And Structures Of New Three-Dimensional Copper Metal-Organic Frameworks, Nitin Kumar Pally

Masters Theses & Specialist Projects

Metal-organic frameworks (MOFs) are crystalline materials with metal ions covalently bonded to organic ligands. The ligands act as spacers often creating a porous structure with very high pore volume and surface area. MOFs are known for their robust structures, high porosity, and different chemical functionalities and are considered for applications in adsorptions, separations, catalysis and gas storage. This work focuses on the synthesis of new MOFs using copper compounds. Different types of carboxylate ligands were used for the synthesis. Two new copper-organic frameworks, [Cu₃(pyz)(btc)] (1), and [(Cu₃(btc))•xH₂O] (2) (btc= benzene-1,3,5-tricarboxylate, pyz= pyrazine) have been …

Phosphate Esters, Thiophosphate Esters And Metal Thiophosphates As Lubricant Additives, David W. Johnson, John E. Hils

Chemistry Faculty Publications

Phosphate esters, thiophosphate esters and metal thiophosphates have been used as lubricant additives for over 50 years. While their use has been extensive, a detailed knowledge of how they work has been a much more recent development. In this paper, the use of phosphate esters and thiophosphate esters as anti-wear or extreme pressure additives is reviewed with an emphasis on their mechanism of action. The review includes the use of alkyl phosphates, triaryl phosphates and metal containing thiophosphate esters. The mechanisms of these materials interacting with a range of iron and steel based bearing material are examined.

Assessing Different Zeolitic Adsorbents For Their Potential Use In Kr And Xe Separation, Breetha Alagappan

UNLV Theses, Dissertations, Professional Papers, and Capstones

Separation of Kr from Xe is an important problem in spent nuclear fuel fission gas management. The energy intensive and expensive cryogenic distillation method is currently used to separate these gases. In this thesis, we have carried out the research into appropriate sorbents for the separation of Kr and Xe using pressure swing adsorption. We have examined zeolites using gas adsorption studies as they have the potential to be more cost effective than other sorbents. Zeolites are microporous aluminosilicates and have ordered pore structures. The pores in zeolites have extra-framework cations are substantially free to move. The mobility of cations …

Synthesis And Characterization Of 2,2-Cis-[Rh2(Nphcoch3)4]•Ncc6h4r Where R = H, 2-Ch3, 3-Ch3, 4-Ch3 And [Rh2(O2cch3)(Nphcocf3)3], Fredricka F. Quarshie

Electronic Theses and Dissertations

Five novel compounds were synthesized and characterized. Crystal structures were determined using Rigaku Mercury 375/MCCD(XtaLAB mini) diffractometer with graphite monochromated MoKα radiation. The crystal structures of [Rh₂(NPhCOCH₃)₄•xNCC₆H₄R where x = 1 or 2 and R=H, 2-CH₃,3-CH₃ and 4-CH₃ were solved to an R₁ value of less than 5 (R₁= Σ||F_o| - |F_c|| / Σ |F_o|). In each of the nitrile complexes, the rhodium is five or six coordinate and possesses pseudo D_4h symmetry. The complexes were …

Synthesis And Characterization Of A New Cyano-Substituted Tris(Pyrazolyl)Borate And Its Thallium(I) Complex, Bozumeh Som

Electronic Theses and Dissertations

A new cyanoscorpionate - tris(4-cyano-3,5-diphenylpyrazolyl)borate (Tp^Ph2,4CN) has been synthesized and characterized. The thallium complex of this ligand TlTp^Ph2,4CN has also been prepared and characterized by FT-IR, ¹H NMR, and single-crystal X-ray-diffraction. The complex TlTp^Ph2,4CN crystalized in the monoclinic space group C2/c with unit cell a = 14.6697(10) Å, b = 13.9493(10) Å, c = 19.3347(12) Å, and b= 91.761(2)°. Structural comparison of TlTp^Ph2,4CN with analogous complexes demonstrated the effects of both steric and electron-withdrawing substituents on coordination geometry and the electronic properties of the metal ion. There were short contacts between the cyano groups …

Synthesis And Characterization Of Three New Tetrakis(N-Phenylacetamidato) Dirhodium(Ii) Nitrile Complexes, Nkongho Atem-Tambe

Electronic Theses and Dissertations

Three new tetrakis [Rh₂(PhNCOCH₃)₄·xNCR] (R = {2-CH₃}C₆H₄ (x=2), R = {3-CH₃}C₆H₄ (x=1), R = (3-CN)C₆H_4∞ (x=1)) complexes have been synthesized and characterized. These complexes were characterized by IR and ¹H NMR spectroscopies and X-ray crystallography which solved with R₁<0.05.

[Rh₂(PhNCOCH₃)₄·2NC{2-CH₃}C₆H₄] was triclinic (a=9.79Å, b=14.79Å, c=16.36Å, α=103.84⁰, β=99.17⁰, γ=99.77⁰, P-1(#2), μCN=2227.78cm^-1, Rh-Rh=2.42Å, N-C=1.13Å, 1.14Å, Rh-N=2.34Å, 2.35Å, Rh-N-C=151.6⁰, 152.5⁰, Rh-Rh-N=173.0⁰, 174.6⁰).

[Rh₂(PhNCOCH₃)_{4 …}

New Bis(Imino)Pyridine Complexes Of Iron(Ii) And Iron(Iii), And Their Catalytic­ Activity In The Mukaiyama Aldol Reaction, Pushkar Shejwalkar, Nigam Rath, Eike Bauer

Chemistry & Biochemistry Faculty Works

New iron(II) and iron(III) complexes bearing bis(imino)pyridine ligands were synthesized and successfully applied to the Mukaiyama aldol reaction. The two complexes [FeCl2 L] (L = bis(imino)pyridine ligand, 55% isolated yield) and [LFe(μCl)3FeCl3] (76%) were obtained employing FeCl2 and FeCl3 iron sources, respectively, and characterized by elemental analyses, mass spectrometry, IR spectroscopy and, one example, by X-ray diffraction. The two new iron complexes were subsequently employed as catalysts in the Mukaiyama aldol reaction after abstraction of two chlorides by AgSbF6 to obtain the aldol products in 43% to virtually quantitative yield (CH2Cl2 solvent, room temperature, 3.5 to 16 h reaction time). …

Conversion Of Iodide To Hypoiodous Acid And Iodine In Aqueous Microdroplets Exposed To Ozone, Elizabeth A. Pillar, Marcelo I. Guzman, Jose M. Rodriguez

Chemistry Faculty Publications

Halides are incorporated into aerosol sea spray, where they start the catalytic destruction of ozone (O₃) over the oceans and affect the global troposphere. Two intriguing environmental problems undergoing continuous research are (1) to understand how reactive gas phase molecular halogens are directly produced from inorganic halides exposed to O₃ and (2) to constrain the environmental factors that control this interfacial process. This paper presents a laboratory study of the reaction of O₃ at variable iodide (I^–) concentration (0.010–100 μM) for solutions aerosolized at 25 °C, which reveal remarkable differences in the reaction intermediates …

Utilization Of Biomass Derived Furans In Value-Added Organics And Heterogeneous Oxorhenium Catalysts For Deoxydehydration Of Diols, Benjamin L. Wegenhart

Open Access Dissertations

As fossil fuels are depleted, there is a growing focus on renewable chemicals based on biomass materials, including both fuels and chemical feedstocks. Current methods for biomass utilization include biological conversion to produce ethanol and various thermochemical routes (gasification, pyrolysis, liquefaction, hydrothermal treatment, etc.). Furfural is one particular chemical that can be obtained from lignocellulosic biomass in good yields through the dehydration of sugar residues. It can be used as a feedstock for chemicals such as furan and THF, or as a platform molecule for making liquid fuels. The objective of this research is to investigate new pathways for the …

Spectroscopic Characterization Of The Water-Oxidation Intermediates In The Ru-Based Catalysts For Artificial Photosynthesis, Dooshaye Moonshiram

Open Access Dissertations

Utilization of sunlight requires solar capture, light-to-energy conversion and storage. One effective way to store energy is to convert it into chemical energy by fuel-forming reactions, such as water splitting into hydrogen and oxygen. Ruthenium complexes are among few molecular-defined catalysts capable of water splitting. Insight into the mechanism of their action will help to design future robust and economically feasible catalysts for light-to-energy conversion. Mechanistic insights about the design of such catalysts can be acquired through spectroscopic analysis of short-lived intermediates of catalytic water oxidation. Development of time-resolved approaches through stopped flow UV-Vis Spectroscopy to follow the catalysis of …

Spectroscopic And Kinetic Study Of Copper-Exchanged Zeolites For The Selective Catalytic Reduction Of Nox With Ammonia, Shane Adam Bates

Open Access Dissertations

The recent application of metal-exchanged, small-pore zeolites for use in the selective catalytic reduction (SCR) of NO_x with ammonia NH₃ for automotive deNO_x applications has been a great stride in achieving emission standard goals. Copper-exchanged SSZ-13 (Cu-SSZ-13), the small-pore zeolite in this study, has been shown to be very hydrothermally stable and active under conditions presented in the exhaust of the lean-burn diesel engine. In this work, detailed studies were performed to identify many aspects of the active site(s) in Cu-SSZ-13 in order to learn about the standard SCR mechanism.

A series of seven Cu-SSZ-13 samples were …

Structure, Theoretical Studies And Coupling Reactions Of Some New Cyclic Boronic Esters, Andrew Kuttler, Sravanthi Durganala, Albert Fratini, Alexander Morgan, Vladimir Benin

Chemistry Faculty Publications

The present report describes the X-ray structural and theoretical studies of some new pinacolboronate esters, and it also outlines the use of the target structures in Suzuki coupling reactions to produce new aromatic or heteroaromatic esters and amides. X-ray structural analysis of the studied compounds revealed that the pinacolborane ring's position with respect to the benzene ring varies, depending on the particular environment. An ortho-positioned carboxylic ester (methyl ester) causes a nearly perpendicular orientation of the pinacolborane unit with respect to the benzene ring, whereas an ortho-positioned amide (N,N-dimethylamide) causes the pinacolborane unit to orient itself nearly coplanar. A plausible …

Transition Metals As Tools To Probe The Electronic Properties Of Porphyrinoids, Jillian Worlinsky

Chemistry Education Materials

This thesis describes in a number of separate chapters a range of studies that measure the variation of specific physical properties with structural modification of the macrocycles, with a particular focus also on using their coordinated metals as probes. Specifically, the transition metal ions are used as tools for interrogation of the electronic properties of porphyrins and pyrrole-modified porphyrins. With the aim of better understanding the electronic and structural factors that govern the optical responses, axial binding strengths, fragmentation patterns and carbonyl stretching frequencies of meso-tetraarylporphyrins, a rational design of pyrrole-modified metalloporphyrins with designed optical properties is derived.

Io3- And I- Sorption From Groundwater By Layered Double Hydroxides, Abbey Rickelmann, Emily Campbell, Natasha Pence, Tatiana Levitskaia, Sayandev Chatterjee, Frances Smith

STAR Program Research Presentations

Several subsurface water plumes are found at the Hanford U.S. DOE site. These plumes contain many different types of hazardous components including radioactive iodate (IO₃^-) and iodide (I^-), which may have deleterious health effects. To selectively uptake IO₃^- and I^-, inorganic layered double hydroxide (LDH) compounds were synthesized and tested. LDHs are mixed transition metal hydroxides that contain positively charged layers that undergo anion exchange. When LDHs are submerged in the plume water, they can selectively uptake IO₃^- and I^- and remove them from the plume. Raman spectroscopy …